Pattern formation material and pattern formation method

ABSTRACT

A pattern formation material of this invention contains a polymer including a first unit represented by Chemical Formula 1 and a second unit represented by Chemical Formula 2, and an acid generator:wherein R&lt;1 &gt;and R&lt;2 &gt;are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R&lt;3&gt;, R&lt;4&gt;, R&lt;5 &gt;and R&lt;6 &gt;are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R&lt;7 &gt;is a protecting group released by an acid.

BACKGROUND OF THE INVENTION

The present invention relates to method and material for forming a pattern, and more particularly, it relates to a method for forming a resist pattern, used for forming a semiconductor device or a semiconductor integrated circuit on a semiconductor substrate, by using exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band and a pattern formation material used in the method.

Currently, in fabrication of a mass storage semiconductor integrated circuit, such as a 64 Mbit dynamic random access memory (RAM) and a logic device or a system LSI with a 0.25 μm through 0.15 μm rule, a resist pattern is formed by using a chemically amplified resist material including a polyhydroxystyrene derivative and an acid generator as principal constituents with KrF excimer laser (of a wavelength of a 248 nm band) used as exposing light.

Moreover, for fabrication of a 256 Mbit DRAM, a 1 Gbit DRAM or a system LSI with a 0.15 μm through 0.13 μm rule, a pattern formation method using, as exposing light, ArF excimer laser lasing at a shorter wavelength (of a 193 nm band) than the KrF excimer laser is now under development.

The chemically amplified resist material including a polyhydroxystyrene derivative as a principal constituent has high absorbance against light of a wavelength of a 193 nm band because of an aromatic ring included therein. Therefore, exposing light of a wavelength of a 193 nm band cannot uniformly reach the bottom of a resist film, and hence, a pattern cannot be formed in a good shape. Accordingly, the chemically amplified resist material including a polyhydroxystyrene derivative as a principal constituent cannot be used when the ArF excimer laser is used as the exposing light.

Therefore, a chemically amplified resist material including, as a principal constituent, a polyacrylic acid derivative or a polycycloolefin derivative having no aromatic ring is used when the ArF excimer laser is used as the exposing light.

On the other hand, as exposing light for a pattern formation method capable of coping with high resolution, X rays, an electron beam (EB) and the like are being examined.

When the X rays are used as the exposing light, however, there are a large number of problems in the exposure system and preparation of a mask. Also, when the EB is used as the exposing light, the throughput is disadvantageously low, and hence, the EB is not suitable to mass production. Thus, neither the X rays nor the EB is preferred as the exposing light.

Accordingly, in order to form a resist pattern finer than 0.10 μm, it is necessary to use exposing light of a wavelength shorter than that of the ArF excimer laser, such as Xe₂ laser (of a wavelength of a 172 nm band), F₂ laser (of a wavelength of a 157 nm band), Kr₂ laser (of a wavelength of a 146 nm band), ArKr laser (of a wavelength of 134 nm band), Ar₂ laser (of a wavelength of a 126 nm band) and soft-X rays (of a wavelength of a 13, 11 or 5 nm band). In other words, a resist pattern is required to be formed by using exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band.

Therefore, the present inventors have formed resist patterns by conducting pattern exposure using F₂ laser (of a wavelength of a 157 nm band) on resist films formed from conventionally known chemically amplified resist materials respectively including a polyhydroxystyrene derivative represented by Chemical Formula A, a polyacrylic acid derivative represented by Chemical Formula B and a polycycloolefin derivative represented by Chemical Formula C.

Now, a method for forming a resist pattern by using any of the aforementioned conventional chemically amplified resist materials and problems arising in the conventional method will be described with reference to FIGS. 2A through 2D.

First, as shown in FIG. 2A, the chemically amplified resist material is applied on a semiconductor substrate 1 by spin coating and the resultant is heated, so as to form a resist film 2 with a thickness of 0.3 μm. Thereafter, as shown in FIG. 2B, the resist film 2 irradiated with a laser beam 4 through a mask 3 for pattern exposure. Thus, an acid is generated from the acid generator in an exposed portion 2 a of the resist film 2 while no acid is generated in an unexposed portion 2 b of the resist film 2.

Next, as shown in FIG. 2C, the semiconductor substrate 1 is heated with a hot plate at, for example, 100° C. for 60 seconds.

Then, the resist film 2 is developed with an alkaline developer, thereby forming a resist pattern 5.

However, as shown in FIG. 2D, the resist pattern 5 cannot be formed in a good pattern shape, and there remains much scum on the semiconductor substrate 1. Such problems occur not only in using the F₂ laser beam as the exposing light but also in using any of the other light of a 1 nm through 30 nm band or a 110 nm through 180 nm band.

Accordingly, a resist pattern cannot be practically formed by irradiating a resist film formed from any of the aforementioned chemically amplified resist materials with light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band.

SUMMARY OF THE INVENTION

In consideration of the aforementioned conventional problems, an object of the invention is forming a resist pattern in a good pattern shape by using exposing light of a 1 nm through 30 nm band or a 110 nm through 180 nm band with minimally producing scum.

The present inventors have studied the causes of the conventional problems occurring in using the conventional chemically amplified resist materials and have found the following:

First, the chemically amplified resist materials have high absorbance against light of a wavelength of a 1 nm through 180 nm band. For example, a resist film with a thickness of 100 nm formed from the chemically amplified resist material including a polyhydroxystyrene derivative has transmittance of 20% at most against a F₂ laser beam (of a wavelength of a 157 nm band). Therefore, various examination has been made on means for improving the transmittance of a chemically amplified resist material against light of a wavelength of a 1 nm through 180 nm band. As a result, the transmittance of a chemically amplified resist material against light of a wavelength of a 1 nm through 180 nm band can be improved when a unit of a polymer having a cyano group (—C≡N) on its side chain is introduced into a base polymer.

Furthermore, when any of the aforementioned chemically amplified resist materials, particularly the resist material including a polyhydroxystyrene derivative, is irradiated with light of a 1 nm through 180 nm band, a reaction is caused regardless of the function of an acid, so that a hydrogen atom bonded to carbon located at the α-position of the principal chain of the polymer can be released and that polymer radicals from which the hydrogen atoms are released can bond to each other to be crosslinked. As a result, the solubility of an exposed portion of the resist film in a developer is degraded. Therefore, means for preventing the crosslinking reaction of the principal chains of the polymer of the chemically amplified resist material has been variously studied. As a result, it has been found that the crosslinking reaction of the principal chains can be avoided by substituting an alkyl group or a chlorine atom for a hydrogen atom located at the α-position of the principal chain of the polymer.

Moreover, when a cyano group is introduced into a side chain of the polymer, the cyano group interacts with a hydroxyl group based on a hydrogen bond. Therefore, the dry etching resistance and the heat resistance of the resist film can be improved, and an unexposed portion of the resist film can be more effectively prevented from dissolving in a developer, so as to improve the contrast between the exposed portion and the unexposed portion of the resist film.

In addition, when a fluorine atom is introduced into an aromatic ring of the polyhydroxystyrene derivative, the transmittance against light of a wavelength of a 1 nm through 180 nm band can be improved, and the solubility in a developer of a hydroxyl group from which a protecting group is released can be improved. As a result, the contrast in the solubility between the exposed portion and the unexposed portion of the resist film can be improved.

The present invention was devised on the basis of the aforementioned findings, and specifically provides pattern formation materials and methods described below.

The first pattern formation material of this invention comprises a polymer including a first unit represented by Chemical Formula 1 and a second unit represented by Chemical Formula 2; and an acid generator:

wherein R¹ and R² are the same or different and selected from the group consisting of an alkyl group such as a methyl group and an ethyl group, a chlorine atom and an alkyl group including a chlorine atom such as CCl₃; R³, R⁴, R⁵ and R⁶ are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R⁷ is a protecting group released by an acid.

In the first pattern formation material, since the first unit has a cyano group and the second unit has a fluorine atom, the transmittance against light of a wavelength of a 1 nm through 180 nm band is largely improved. Also, since an alkyl group, a chlorine atom or an alkyl group including a chlorine atom is substituted for each hydrogen atom located at the α-positions of the principal chains of the first and second units, the principal chains are not crosslinked, resulting in improving the solubility of an exposed portion of the resist film in a developer. Furthermore, since the second unit has a fluorine atom, the solubility in the developer of a hydroxyl group from which a protecting group is released can be improved. Accordingly, the solubility of the exposed portion of the resist film in the developer can be improved. As a result, the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Moreover, since the second unit has a benzene ring, the dry etching resistance can be improved.

The second pattern formation material of this invention comprises a polymer including a first unit represented by Chemical Formula 3, a second unit represented by Chemical Formula 4 and a third unit represented by Chemical Formula 5; and an acid generator:

wherein R¹, R² and R⁸ are the same or different and selected from the group consisting of an alkyl group such as a methyl group and an ethyl group, a chlorine atom and an alkyl group including a chlorine atom such as CCl₃; R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are a hydrogen atom or a fluorine atom, at least one of R³, R⁴, R⁵ and R⁶ being a fluorine atom; and R⁷ is a protecting group released by an acid.

In the second pattern formation material, since the first unit has a cyano group and the second and third units have a fluorine atom, the transmittance against light of a wavelength of a 1 nm through 180 nm band is largely improved. Also, since an alkyl group, a chlorine atom or an alkyl group including a chlorine atom is substituted for each hydrogen atom located at the α-positions of the principal chains of the first, second and third units, the principal chains are not crosslinked, resulting in improving the solubility of an exposed portion of the resist film in a developer. Furthermore, since the second unit has a fluorine atom, the solubility in the developer of a hydroxyl group from which a protecting group is released can be improved. Accordingly, the solubility of the exposed portion of the resist film in the developer can be improved. As a result, the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Moreover, since the second and third units have a benzene ring, the dry etching resistance can be largely improved. In addition, since the third unit has a phenyl group, the wettability is improved so as to improve the adhesion to the substrate, and the dissolving rate in an alkaline developer can be controlled by adjusting the ratio of the third unit included in the polymer.

The third pattern formation material of this invention comprises a polymer including a first unit represented by Chemical Formula 6, a second unit represented by Chemical Formula 7 and a third unit represented by Chemical Formula 8; and an acid generator:

wherein R¹, R² and R¹³ are the same or different and selected from the group consisting of an alkyl group such as a methyl group and an ethyl group, a chlorine atom and an alkyl group including a chlorine atom such as CCl₃; R³, R⁴, R⁵ and R⁶ are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R⁷ is a protecting group released by an acid.

In the third pattern formation material, since the first unit has a cyano group and the second unit has a fluorine atom, the transmittance against light of a wavelength of a 1 nm through 180 nm band is largely improved. Also, since an alkyl group, a chlorine atom or an alkyl group including a chlorine atom is substituted for each hydrogen atom located at the α-positions of the principal chains of the first, second and third units, the principal chains are not crosslinked, resulting in improving the solubility of an exposed portion of the resist film in a developer. Furthermore, since the second unit has a fluorine atom, the solubility in the developer of a hydroxyl group from which a protecting group is released can be improved. Accordingly, the solubility of the exposed portion of the resist film in the developer can be improved. As a result, the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Moreover, since the second unit has a benzene ring, the dry etching resistance can be improved. Also, since the third unit has a carboxyl group, carboxylic acid is generated in the exposed portion of the resist film through irradiation with light, resulting in improving the contrast between the exposed portion and the unexposed portion of the resist film.

The fourth pattern formation material of this invention comprises a polymer including a first unit represented by Chemical Formula 9, a second unit represented by Chemical Formula 10 and a third unit represented by Chemical Formula 11; and an acid generator:

wherein R¹, R⁸ and R¹⁴ are the same or different and selected from the group consisting of an alkyl group such as a methyl group and an ethyl group, a chlorine atom and an alkyl group including a chlorine atom such as CCl₃; R⁹, R¹⁰, R¹¹ and R¹² are a hydrogen atom or a fluorine atom; and R¹⁵ is a protecting group released by an acid.

In the fourth pattern formation material, since the first unit has a cyano group and the second unit has a fluorine atom, the transmittance against light of a wavelength of a 1 nm through 180 nm band is largely improved. Also, since an alkyl group, a chlorine atom or an alkyl group including a chlorine atom is substituted for each hydrogen atom located at the α-positions of the principal chains of the first, second and third units, the principal chains are not crosslinked, resulting in improving the solubility of an exposed portion of the resist film in a developer. Furthermore, since the second unit has a fluorine atom, the solubility in the developer of a hydroxyl group from which a protecting group is released can be improved. Accordingly, the solubility of the exposed portion of the resist film in the developer can be improved. As a result, the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Moreover, since the second unit has a benzene ring, the dry etching resistance can be improved. Also, since the second unit has a phenyl group, the wettability is improved so as to improve the adhesion to the substrate. Furthermore, the dissolving rate in an alkaline developer can be controlled by adjusting the ratio of the second unit included in the polymer. In addition, since carboxylic acid is generated in the exposed portion of the resist film when an acid is generated through irradiation with light so as to release the protecting group from the third unit, the contrast between the exposed portion and the unexposed portion of the resist film can be improved.

Specific examples of the protecting group released by an acid represented by R⁷ in the aforementioned formulas are represented by Chemical Formula D:

Also, specific examples of the protecting group released by an acid represented by R¹⁵ in the aforementioned formulas are represented by Chemical Formula E:

The first pattern formation method of this invention comprises the steps of forming a resist film by applying, on a substrate, the first pattern formation material; irradiating the resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing the resist film after the pattern exposure.

In the first pattern formation method, since the first pattern formation material is used, the transmittance against light of a wavelength of a 1 nm through 180 nm band can be largely improved, the solubility of an exposed portion of the resist film in a developer can be improved, the dry etching resistance can be improved, and the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved.

The second pattern formation method of this invention comprises the steps of forming a resist film by applying, on a substrate, the second pattern formation material; irradiating the resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing the resist film after the pattern exposure.

In the second pattern formation method, since the second pattern formation material is used, the transmittance against light of a wavelength of a 1 nm through 180 nm band can be largely improved, the solubility of an exposed portion of the resist film in a developer can be improved, the dry etching resistance can be improved, and the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Furthermore, the wettability of the pattern formation material is improved so as to improve the adhesion to the substrate, and the dissolving rate in an alkaline developer can be controlled by adjusting the ratio of the third unit included in the polymer.

The third pattern formation method of this invention comprises the steps of forming a resist film by applying, on a substrate, the third pattern formation material; irradiating the resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing the resist film after the pattern exposure.

In the third pattern formation method, since the third pattern formation material is used, the transmittance against light of a wavelength of a 1 nm through 180 nm band can be largely improved, the solubility of an exposed portion of the resist film in a developer can be improved, the dry etching resistance can be improved, and the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Furthermore, since carboxylic acid is generated in the exposed portion of the resist film through irradiation with light, the contrast between the exposed portion and the unexposed portion of the resist film can be improved.

The fourth pattern formation method of this invention comprises the steps of forming a resist film by applying, on a substrate, the fourth pattern formation material; irradiating the resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing the resist film after the pattern exposure.

In the fourth pattern formation method, since the fourth pattern formation material is used, the transmittance against light of a wavelength of a 1 nm through 180 nm band can be largely improved, the solubility of an exposed portion of the resist film in a developer can be improved, the dry etching resistance can be improved, and the contrast in the solubility between the exposed portion and an unexposed portion of the resist film can be largely improved. Furthermore, the wettability of the pattern formation material is improved so as to improve the adhesion to the substrate, and the dissolving rate in an alkaline developer can be controlled by adjusting the ratio of the second unit included in the polymer. Moreover, since carboxylic acid is generated in the exposed portion of the resist film through irradiation with light, the contrast between the exposed portion and the unexposed portion can be improved.

In any of the first through fourth pattern formation methods, the exposing light is preferably F₂ excimer laser, Ar₂ excimer laser or soft-X rays.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, 1C and 1D are cross-sectional views for showing procedures in a pattern formation method according to any of Embodiments 1 through 4 of the invention; and

FIGS. 2A, 2B, 2C and 2D are cross-sectional views for showing procedures in a conventional pattern formation method.

DETAILED DESCRIPTION OF THE INVENTION Embodiment 1

A pattern formation material and a pattern formation method according to Embodiment 1 of the invention will now be described with reference to FIGS. 1A through 1D.

In this embodiment, the first pattern formation material and the first pattern formation method described above are embodied, and the specific composition of a resist material of this embodiment is as follows:

Base polymer: a polymer represented by Chemical Formula F below

Acid generator: triphenylsulfonium triflate (1 wt % based on the base polymer)

Solvent: diglime

First, as shown in FIG. 1A, the resist material having the above-described composition is applied on a semiconductor substrate 10 by spin coating, thereby forming a resist film 11 with a thickness of 0.2 μm. At this point, since the base polymer is alkali-refractory, the resist film 11 is alkali-refractory.

Next, as shown in FIG. 1B, the resist film 11 is subjected to pattern exposure by irradiating through a mask 12 with F₂ excimer laser 13 (of a wavelength of a 157 nm band). Thus, an acid is generated from the acid generator in an exposed portion 11 a of the resist film 11 while no acid is generated in an unexposed portion 11 b of the resist film 11.

Then, as shown in FIG. 1C, the semiconductor substrate 10 together with the resist film 11 is heated with a hot plate 14. Thus, the base polymer is heated in the presence of the acid in the exposed portion 11 a of the resist film 11, so as to release a protecting group of a unit on the right hand side in Chemical Formula F. As a result, the base polymer becomes alkali-soluble.

Subsequently, the resist film 11 is developed with an alkaline developer such as a tetramethylammonium hydroxide aqueous solution. Thus, the exposed portion 11 a of the resist film 11 is dissolved in the developer, so that a resist pattern 15 can be formed from the unexposed portion 11 b of the resist film 11 as shown in FIG. 1D.

Embodiment 2

A pattern formation material and a pattern formation method according to Embodiment 2 of the invention will now be described. Embodiment 2 is different from Embodiment 1 in the resist material alone, and hence, the resist material alone will be herein described.

In this embodiment, the second pattern formation material and the second pattern formation method described above are embodied, and the specific composition of the resist material is as follows:

Base polymer: a polymer represented by Chemical Formula G below

Acid generator: triphenylsulfonium triflate (1 wt % based on the base polymer)

Solvent: diglime

Embodiment 3

A pattern formation material and a pattern formation method according to Embodiment 3 of the invention will now be described. Embodiment 3 is different from Embodiment 1 in the resist material alone, and hence, the resist material alone will be herein described.

In this embodiment, the third pattern formation material and the third pattern formation method described above are embodied, and the specific composition of the resist material is as follows:

Base polymer: a polymer represented by Chemical Formula H below

Acid generator: triphenylsulfonium triflate (1 wt % based on the base polymer)

Solvent: diglime

Embodiment 4

A pattern formation material and a pattern formation method according to Embodiment 4 of the invention will now be described. Embodiment 4 is different from Embodiment 1 in the resist material alone, and hence, the resist material alone will be herein described.

In this embodiment, the fourth pattern formation material and the fourth pattern formation method described above are embodied, and the specific composition of the resist material is as follows:

Base polymer: a polymer represented by Chemical Formula I below

Acid generator: triphenylsulfonium triflate (1 wt % based on the base polymer)

Solvent: diglime 

What is claimed is:
 1. A pattern formation material comprising: a polymer including a first unit represented by Chemical Formula 1 and a second unit represented by Chemical Formula 2; and an acid generator;

 wherein R¹ and R² are the same or different and selected from the group consisting of a chlorine atom and an alkyl group including a chlorine atom; R³, R⁴, R⁵ and R⁶ are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R⁷ is a protecting group released by an acid.
 2. A pattern formation material comprising: a polymer including a first unit represented by Chemical Formula 3, a second unit represented by Chemical Formula 4 and a third unit represented by Chemical Formula 5; and an acid generator:

 wherein R¹, R² and R⁸ are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are a hydrogen atom or a fluorine atom, at least one of R³, R⁴, R⁵ and R⁶ being a fluorine atom; and R⁷ is a protecting group released by an acid.
 3. A pattern formation material comprising: a polymer including a first unit represented by Chemical Formula 6, a second unit represented by Chemical Formula 7 and a third unit represented by Chemical Formula 8; and an acid generator:

 wherein R¹, R² and R¹³ are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R³, R⁴, R⁵ and R⁶ are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R⁷ is a protecting group released by an acid.
 4. The pattern formation material of claim 3, wherein R⁷ in said Chemical Formula 7 is one of the following protecting groups,


5. A pattern formation material comprising: a polymer including a first unit represented by Chemical Formula 9, a second unit represented by Chemical Formula 10 and a third unit represented by Chemical Formula 11; and an acid generator:

 wherein R¹, R⁸ and R¹⁴ are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R⁹, R¹⁰, R¹¹ and R¹² are a hydrogen atom or a fluorine atom; and R¹⁵ is a protecting group released by an acid.
 6. The pattern formation material of claim 5, wherein R¹⁵ in said Chemical Formula 11 is one of the following protecting groups,


7. A pattern formation method comprising the steps of: forming a resist film by applying, on a substrate, a pattern formation material containing a polymer including a first unit represented by Chemical Formula 1 and a second unit represented by Chemical Formula 2, and an acid generator:

 wherein R¹ and R² are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R³, R⁴, R⁵ and R⁶ are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R⁷ is a protecting group released by an acid; irradiating said resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing said resist film after the pattern exposure.
 8. The pattern formation method of claim 7, wherein said exposing light is Xe₂ laser, F₂ laser, Kr₂ laser, ArKr laser, Ar₂ laser or soft-x-rays.
 9. The pattern formation method of claim 7, wherein said polymer is,


10. A pattern formation method comprising the steps of: forming a resist film by applying, on a substrate, a pattern formation material containing a polymer including a first unit represented by Chemical Formula 3, a second unit represented by Chemical Formula 4 and a third unit represented by Chemical Formula 5, and an acid generator:

 wherein R¹, R² and R⁸ are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R³, R⁴, R⁵, R⁶, R⁹, R¹⁰, R¹¹ and R¹² are a hydrogen atom or a fluorine atom, at least one of R³, R⁴, R⁵ and R⁶ being a fluorine atom; and R⁷ is a protecting group released by an acid; irradiating said resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing said resist film after the pattern exposure.
 11. The pattern formation method of claim 10, wherein said exposing light is Xe₂ laser, F₂ laser, Kr₂ laser, ArKr laser, Ar₂ laser or soft-x-rays.
 12. The pattern formation method of claim 10, wherein said polymer is,


13. A pattern formation method comprising the steps of: forming a resist film by applying, on a substrate, a pattern formation material containing a polymer including a first unit represented by Chemical Formula 6, a second unit represented by Chemical Formula 7 and a third unit represented by Chemical Formula 8, and an acid generator:

 wherein R¹, R² and R¹³ are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R³, R⁴, R⁵ and R⁶ are a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom; and R⁷ is a protecting group released by an acid; irradiating said resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing said resist film after the pattern exposure.
 14. The pattern formation method of claim 13, wherein said exposing light is Xe₂ laser, F₂ laser, Kr₂ laser, ArKr laser, Ar₂ laser or soft-x-rays.
 15. The pattern formation method of claim 13, wherein said polymer is,


16. The pattern formation method of claim 13, wherein R⁷ in said Chemical Formula 7 is one of the following protecting groups,


17. A pattern formation method comprising the steps of: forming a resist film by applying, on a substrate, a pattern formation material containing a polymer including a first unit represented by Chemical Formula 9, a second unit represented by Chemical Formula 10 and a third unit represented by Chemical Formula 11, and an acid generator:

 wherein R¹, R⁸ and R¹⁴ are the same or different and selected from the group consisting of an alkyl group, a chlorine atom and an alkyl group including a chlorine atom; R⁹, R¹⁰, R¹¹ and R¹² are a hydrogen atom or a fluorine atom; and R¹⁵ is a protecting group released by an acid; irradiating said resist film with exposing light of a wavelength of a 1 nm through 30 nm band or a 110 nm through 180 nm band for pattern exposure; and forming a resist pattern by developing said resist film after the pattern exposure.
 18. The pattern formation method of claim 17, wherein said exposing light is Xe₂ laser, F₂ laser, Kr₂ laser, ArKr laser, Ar₂ laser or soft-x-rays.
 19. The pattern formation method of claim 17, wherein said polymer is,


20. The pattern formation material of claim 17, wherein R¹⁵ in said Chemical Formula 7 is one of the following protecting groups, 